Vanadium organometallic compounds and polymerization catalysts thereof

ABSTRACT

The reaction product of a sulfur-containing vanadium salt such as vanadyl sulfate and an organophosphate, such as triethyl phosphate, results in a hydrocarbon soluble catalyst component. This component forms an active vanadium coordination catalyst when combined with an organoaluminum halide. The resulting vanadium coordination catalyst is especially useful in the production of &#39;&#39;&#39;&#39;EP&#39;&#39;&#39;&#39; and &#39;&#39;&#39;&#39;EPDM&#39;&#39;&#39;&#39; rubber.

Huerta et al.

VANADIUM ORGANOMETALLIC COMPOUNDS AND POLYMERIZATION CATALYSTS THEREOF Inventors: James R. Huerta, Adrian; Jeffrey G.

Meyer, Chelsea, both of Mich.

Assignee:

Calif.

Filed: Dec. 30, 1970 Appl. No.: 102,948

Related U.S. Application Data Division of Ser. No. 846,614, July 31, 1969, Pat. No. 3,595,844.

Field of Search.....260/429 K, 429 R; 252/431 P Dart Industries, Inc., Los Angeles,

111 1 3,725,444 1 Apr. 3, 1973 [56] References Cited UNITED STATES PATENTS 3,076,830 2/ 1963 Conn ..260/429 R 3,290,342 l2/1966 Stern et al ..260/429 R 3,595,844 7/1971 Huerta et al. ..252/43l P Primary ExaminerDaniel E. Wyman Assistant Examiner-A. P. Demers Attorney-Fred S. Valles and Richard A. Dannells, Jr.

[57] ABSTRACT The reaction product of a sulfur-containing vanadium salt such as vanadyl sulfate and an organophosphate, such as triethyl phosphate, results in a hydrocarbon soluble catalyst component. This component forms an active vanadium coordination catalyst when combined with an organoaluminum halide. The resulting vanadium coordination catalyst is especially useful in the production of EP and EPDM" rubber.

4 Claims, No Drawings VANADIUM ORGANOMETALLIC COMPOUNDS AND POLYMERIZATION CATALYSTSTHEREOF This application is a division of pending application, Ser. No. 846,614 filed July 31, 1969, now U. S. Pat. No. 3,595,844.

BACKGROUND OF THE INVENTION 1. Field of the Invention catalyst This invention is directed to a novel vanadium organometallic composition of matter and a process for its synthesis, a novel catalvst which includes this composition and a process using the catalyst. More particularly, the invention relates to a hydrocarbon soluble vanadium organometallic compound which when combeen disclosed in theprior art; .see U. S- Pat. Nos.

3,113,115 and 3,297,733 and 3,361,779. f the organometallic compounds disclosed, particular attention has been given to those in which thetransition metal constituent is vanadium; see U. S. Pat. Nos. 3,294,828 and 3,361,778. Coordinationcatalysts containing such prior art vanadium organometallic compounds'as vanadium tetrachlorides and vanadium oxytrichlorides, and compounds capable of reducing the vanadium to a valance state of less than 3, such as the organoaluminum compounds, have long been of interest for use as polymerization catalysts;-see U. S. Pat. No. 2,962,451. This interest in developing novel vanadium-containing coordination catalysts is evidenced by the considerable number of recent patents on the subject; see, for example, U. S. Pat. Nos. 3,392,160 and 3,396,155 and 3,427,257. Particular attention has been shown in the preparation of alphaolefin polymers, copolymers of alpha-olefins, e.g., ethylene/propylene (EP) rubber, and the terpolymers of the alpha-olefins with the nonconjugated dienes, e.g., ethylene/propylene/diene terpolymers, (EPDM) rubber. Vanadium coordination catalysts have been disclosed as having activity for the preparation of EP andEPDM rubber; see U. S. Pat. Nos. 3,116,517 and 3,234,383.

SUMMARY OF THE INVENTION ganophosphate compound has the formula:

0 (Kohl wherein R is an alkyl or an alkyl ether having one to 16 carbon atoms or an aryl having up to 16 carbon atoms Name of Compound Fonnula I Ammonium Divanadyl Sulfate (NH,),SO. 2VOSO, H,O Potassium Divanadyl Sulfate l(,S0,-2VOSO Sodium Divanadyl Sulfate Ammonium Vanadyl Disulfate Potassium vanadyl Disulfate Sodium Vanadyl Disulfate NaSOgVOSOMl-LO Vanadium Trioxydisulfate V,O,( 50,)2 Vanadium Dioxytrisulfate V,O,( SO

Ammonium Vanadium Tetroxydisulfate [(Nl-L) V0,SO,-2H,O] Potassium Vanadium Tetroxydisulfate [KVO,SO,-3H,O], vanadyl Dihydrosulfate 2( VO)SO -I-I,SO Ammonium Vanadous Sulfate (NH )V(S0,) ,-12H,0 Sodium Vanadous Sulfate NaV( SO ),-l 2H,O Potassium Vanadous Sulfate KV(SO,),-12H,O

- Vanadous Sulfate V,(SO )3 The reaction between the-vanadium salt and the organo-phosphate compound as defined in the above paragraphyields a product which is believed to have a formula at least similar to those .formulas included in the equations set forth hereinbelow illustrating the synthesis routes of certain embodiments of the vanadium organometallic compounds of the present invention. However, the exact formulas for the active vanadium organometallic compounds are not critical to this invention. The critical feature of this invention is to produce a vanadium compound or compounds which are highly soluble in the hydrocarbon media used as a diluent in the polymerization of the alpha-olefins and dienes of the type enumerated hereinbelow. It has been a trialkyl, trialkyl ether or triaryl phosphate to' yield the vanadium organometallic compound of this invention and a side-product of an ether. The route is believed to be represented by the following equation:

Another route comprises reacting one mole of vanadyl sulfite with at least two moles of the foregoing organophosphate compound to yield the vanadium organometallic compound of this invention and a sideproduct of an ether as indicated by the following equation:

O VOSOa 2(R0hl The vanadium organometallic compounds of this invention can also be synthesized by reacting the organophosphate compound as defined above with the reactants used to form the sulfur-containing vanadium salts. For example, it is well known to produce vanadyl sulfate from ammonium meta-vanadate, sulfuric acid and sulfur dioxide. Thus another route to this compound can be represented by the following equation:

. the organophosphate as defined above as indicated by the following equation:

The vanadium coordination catalysts of this invention are obtained by using the vanadium organometallic-containing reaction product described herein with at least one organoaluminum halide reducing compound in the presence of an inert liquid organic medi um. Representative types of organoaluminum compounds include dialkylaluminum monohalides; alkylaluminum dihalides; and aluminum alkyl, cycloalkyl or aryl sesquihalides. Particularly preferred organoaluminum halide compounds in combination with the vanadium organometallic reaction products of this invention include diethylaluminum monochloride and ethylaluminum sesquichloride. Other or organoaluminum compounds suitable for the coordination catalyst of this invention include methyl, propyl and isobutyl aluminum chlorides. 1

Although the relative proportions of ,the vanadiu organo-metallic component and the organoaluminum halide component can vary widely and one of ordinary skill in the art can readily determine the optimum proportions for specific vanadium and aluminum compounds by routine experimentation, one would generally operate with an A l :V molar ratio in the range ofaboutlzl to :1.

The vanadium coordination catalysts of this invention are especially useful in the preparation of polymers of ethylene, propylene and similar alpha-olefins having the formula: I

R--CH#IH,

wherein R is hydrogen or a hydrocarbon radical, particularly an unsaturated alkyl hydrocarbon radical having one to eight carbon atoms, e.g., butene-l; hexene-l; 4-methylpentene-l; heptene-l S-methyl-hexene-l; octene-l; 4-ethylhexene-l; l-nonene; l-decene, and dienes, e.g., butadiene and the like. The catalyst of this invention is especially useful in the copolymerization of ethylene and propylene to yield rubbery products and the production of unsaturated, sulfur-vulcanizable, rubbery terpolymers of ethylene and propylene and a nonconjugated diene, e.g., dicyclopentadiene (DCP); methyl-cyclopentadiene; methylene norbornene (N MB); 1,5-cyclooctadiene; 1.4-hexadiene; or other copolymerizable dienes. The unique features of the vanadium coordination catalyst of this invention are high productivity of the catalyst in terms of the amount of product per pound of catalyst, low cost, ease of handling and storage, and very high solubility in hydrocarbon solvents.

PREFERRED EMBODIMENTS OF THIS INVENTION 7 In a preferred embodiment of this invention, the vanadium coordination catalyst comprises an admixture of an organo-aluminum halide and the reaction product of vanadyl sulfate and the organophosphate compound having the formula set forth above in SUM- MARY OF THE INVENTION wherein R is an alkyl having one to eight carbon atoms. The reaction takes place at a temperature in the range of about 50 to 200 C and at subatmospheric to atmospheric or above for a period of about 5 minutes to several hours. At temperatures below 50little if any reaction takes place and above 200 C the products have a tendency to decompose. The stoichiometrical minimum molar ratio of the organophosphate compound to the sulfur-containing vanadium salt in the reactants is about 2:1, although the reaction is preferably carried out in the molar range of about 2:] to 20:1 and even higher and still more preferably in the molar range of about 5:1 to l5:l. An excess amount of the phosphorus compound is employed to keep the vanadium organometallic product in solution.

To obtain the preferred vanadium organometallic component, 1 mole of vanadyl sulfate is reacted with at least 2 moles of trimethyl, triethyl, tripropyl or tributyl phosphate or mixtures thereof at a temperature inthe range of to 200 C and atmospheric pressure for about 1 to 20 hours. The following theoretical equation In the preferred embodiment of this invention, the entire reaction product can be used as the vanadium component of the coordination 'catalystof this invention because the reaction described in the preceding paragraph takes place at such a rapid rate. This results in very little side products being formed during the reaction and those that are formed are soluble in the organophosphate, e.g., triethyl phosphate.

It is preferred to separate out the solid residue containing the unreacted vanadium salt from the solution comprising the vanadium organometallic'compound dissolved in the organo-phosphate compound. The large amount of excess organophosphate used in the reaction as well as the volatile side-products, e.g., ethersand any water of hydration that may be present, are preferably stripped or otherwise removed from the reaction product to increase the vanadium content to reasonable levels for polymerization such as at least 0.5

percent by weight, preferably 5 higher vanadium content.

In another embodiment of the present invention, the vanadium coordination catalyst comprises an admixture of an organoaluminum halide and the reaction product of one mole of ammonium meta-vanadate with at least one mole of sulfur dioxide and at least two moles of the organophosphate compound having the formula set forth above wherein R is an alkyl having one to eight carbon atoms at the same operating conditions set forth above in connection with the preferred embodiment.

In the case of the embodiment of the preceding paragraph and in the case of other reactions where there is a greater tendency to form insoluble side products, the resulting vanadium organometallic compounds can be separated from the reaction product mixture as a crystalline solid. Such a separation is also desirable even in the case of the preferred embodiment where the synthesis of the vanadium organometallic compound is performed at a location distant from where the polymerization is carried out. To achieve this percent by weight or separation, the reaction product is cooled, the excess solid reactants and insoluble products are removed, for example, by filtration, and the filtrate containing the organophosphate compound and the organometallic compound dissolved therein is stripped, preferably under a vacuum to avoid decomposition of the product. The resultant liquid productthat may still contain impurities can then be solubilized in a suitable solvent, filtered, vacuum stripped to remove the solvent and then crystallized to yield a crystalline product. The crystallization takes place by cooling the stripped product or by other known techniques. Suitable solvents for the crystallization of the vanadium organo-metallic compound of this invention include low boiling paraffinic hydrocarbons such as pentane, hexane, heptane and the like.

Either the solution of the vanadium organometallic or the purified solid crystalline material is then combined in situ in thepolymerization reactor with one .or more of the organoaluminum halide compounds .set forth above in SUMMARY OF THE INVENTION. Examples of the preferred organoaluminum halide compound which is combined with the preferred vanadium 0rgano-metallic. compound include ethylaluminum sesquichloride and diethylaluminum mono'chloride in a molar ratio in the range of about 4:1 to I021.

Inert liquid organic media, i.e., liquids which do not interfere with the desired polymerization reaction, which are suitably present in the polymerization reactor with the vanadium coordination catalysts of this invention include tetrachloroethylene; aromatic solvents such as benzene, toluene and xylenes; saturated aliphatic hydrocarbon and cycloaliphatic hydrocarbons such as cyclohexane, butane, neopentane, isopentane, n-pentane, cyclopentane, hexane, heptane, methylcyclohexane, 2,2,4-trimethylpentane, octane, and nonane; chlorinated aliphatic hydrocarbons & chlorinated cycloaliphatic hydrocarbons such as carbon tetrachloride, ethyl chloride, methyl chloride, 1,2- dichloroethane and trichloromonofluoromethane; and the organic phosphorus compounds as described above. Particularly effective solvents for the preferred vanadium coordination catalysts of this invention are saturated aliphatic and cycloaliphatic hydrocarbons especially n-hexane, n-heptane, cyclohexane and cycloheptane.

The vanadium coordination catalysts of this invention are employed by contacting them with one or more of the monomers described in SUMMARY OF THE INVENTION at subatmospheric to above atmospheric pressure and at a temperature of about 50 C to 100 C. Preferably the conditions for polymerizing these monomers comprise from about atmospheric pressure to about 15 atmospheres and a temperature of about -5 to 50 C. It has been found for the vanadium coordination catalysts of this invention that at temperatures above 25 C the product yields tend to decrease at pressures in the range of about 25 to 125 psig.

The polymerization reaction is arrested and the product is precipitated out of solution by the addition of a non-solvent such as an alcohol. The product is then washed, filtered, and dried. An antioxidant, such as butylated hydroxytoluene, is optionally added to the product prior to the recovery step to avoid its oxidation and degradation.

The polymerization reaction can either be carried out in a batch or continuous operation. In the continuous process, the solvent, vanadium coordination catalyst and monomers are continuously introduced into a polymerization zone which is equipped with means for agitation at a sufficient rate to provide the residence time required for the desired polymer concentration in the reactor effluent.

The vanadium coordinationcatalyst of this invention are especially useful in the preparation of EP and EPDM rubbers. The ethylene content of these rubbery products ranges from between about 20 and weight percent and correspondingly, the propylene content ranges from between 30 and weight percent-In the case of EPDM, the amount of diene should exceed 1 weight percent of the final product and preferably ranges between about 3 and 30 weight percent. Accordingly, the ethylene and propylene in the final terpolymer ranges between about 70 and 97 weight per-' The foregoing EP and EPDM rubbers are prepared by reacting, preferably in the presence of hydrogen or other known chain transfer agents, a monomeric mixture of ethylene and propylene comprising from about 20 to 70 weigh percent ethylene and 30 to 80 weight percent propylene and, in the case of EPDM rubber, the nonconjuga'ted diene in a reaction zone in the presence of an inert solvent at a temperature of '5 to 50 C with a catalytic amount of one of the vanadium coordination catalysts of this invention.

The examples below illustrate the methods of preparation of some of the embodiments of the present invention and their use in polymerization.

EXAMPLE 1 Preparation of Solid Vanadium Organometallic Catalyst Component from Vanadyl Sulfate tants were heated to reflux temperatures of about 200 C and held at this temperature under atmospheric pressure for about one hour. After the resulting product mixture was cooled to room temperature, 8.3 grams of the excess vanadyl sulfate were filtered off, representing about 58 percent by weight conversion of the vanadium in the reaction mixture to the desired product. The filtrate was vacuum stripped at mm Hg. and 130 C to yield 25 grams of solid residue. Recrystallization of this solid residue from benzene produced light blue prismatic crystals having a vanadium content of 9.3 weight percent (11.24 percent theoretical).

EXAMPLE 2 Use of Solid Vanadium Organometallic Catalyst Component of Example 1 in Preparation of EP Rubber at 25 C.

A stirred glass-bowl reactor was charged with 30 psi of ethylene, 1300 cc of heptane and 320 cc of liquid propylene. During the course of the reaction, 0.45 grams of the vanadium Organometallic compound obtained from Example 1 dissolved in 30 cc of benzene and 1.2 grams of ethylaluminum sesquichloride dissolved in 30 cc of n-heptane were continuously metered into the reactor. The reaction mixture was maintained at a temperature of 25 C and a constant pressure of 60 psig with a gas mixture comprising 60 mole percent ethylene and 40 mole percent propylene. The reaction was terminated and the ethylene/propylene copolymer was precipitated out of solution by the addition of an excess amount of isopropyl alcohol after a total reaction time of 35 minutes. The resulting copolymer product was filtered, dried and weighed. The yield of the ethylene/propylene copolymer product was 85 grams. This yield corresponds to a productivity of about 189 grams of polymer product per gram of the solid vanadium Organometallic compound of this invention or about 20,300 grams of polymer product per gram of vanadium.

EXAMPLE 3 Use of Vanadium Tetrachloride in the Preparation of EP'Rubber at 25 C as a Control ethylene/propylene copolymer product for the control run was 106 grams.

EXAMPLE 4 Use of Solid Vanadium Organometallic of Example 1 in Preparation of EP Rubber at 40 C when operating with the catalyst of this invention was 44 grams.

EXAMPLE 5 Preparation of a Solution of Vanadium Organometallic Catalyst Component from Vanadyl Sulfate 39.8 grams (0.244 mole) of vanadyl sulfate and 364 grams (2.0 moles) of triethyl phosphate were charged to a 1 liter reactor equipped with a reflux condenser, mechanical stirrer and thermometer. The reactants were heated to 137 C and held at this temperature under atmospheric pressure for about 20 minutes during which time the vanadyl sulfate appeared to go into solution. The temperature in the reactor was lowered to C for 2 hours and the resulting product was filtered without yielding a residue. The liquid product mixture was partially stripped under a vacuum of 10 mm Hg. and a temperature of C to remove 90 percent by weight of the excess triethyl phosphate. Benzene was added to the partially stripped reaction product and the resulting solution was filtered at room temperature. The resulting filtrate was vacuum stripped at the above conditions to yield 105.8 grams of dark green liquid which contained about 5.3 percent by weight vanadium.

EXAMPLE 6 Use of the Solution of Vanadium Organometallic Catalyst Component of Example 5 in Preparation of EP Rubber at 25 C The same procedure was followed in this run that was used in Example 2 except that 0.79 grams of the dark green solution of the Organometallic compound of Example 5 dissolved in 30 cc of benzene were used. The difference in the amount of the solution of the catalyst component used in this Example versus that of the solid vanadium organophosphate catalyst component used in Example 2 was the amount necessary to put them on an equivalent vanadium content. The yield of the-vanadium coordination catalyst of this invention was 84 grams. This yield corresponds to about the same productivity as that of the vanadium Organometallic catalyst component of Example 2.

EXAMPLE 7 Preparation of a Solution of Vanadium Organometallic Catalyst Component with Great Excess of Triethyl Phosphate 400 grams (2.45 moles) of vanadyl sulfate and 6,000 (32.9 moles) grams of triethyl phosphate were charged to a 12 liter reactor equipped with a reflux condenser, mechanical stirrer and thermometer. The reactants were heated to 130 C and held at this temperature under atmospheric pressure for about 3 hours. The reaction product mixture was partially stripped under a vacuum of 10 mm Hg. to remove 4,000 grams of excess triethyl phosphate. The partially stripped reaction product mixture was cooled to room temperature and filtered to remove 84.4 grams of a green precipitate. The resulting filtrate was vacuum stripped at the above conditions to remove an additional 1,000 grams of triethyl phosphate. The final reaction product mixture was a clear, dark blue, slightly viscous liquid weighing about l220 grams and containing 7.07 percent by weight vanadium. An analysis of the final liquid product mixture showed that it contained about 63 percent by weight of the crystalline solid of the type produced in Example 1 dissolved in excess triethyl phosphate. The characteristic light blue prismatic crystals were precipitated out on cooling this mixture to C. The crystals dissolved on reheating toroom temperature.

EXAMPLE 8 Use of the Solution of Vanadium Organom etallic Catalyst Component of Example 7 in Preparation of EP Rubber at 25C The same procedure was followed in this run .that was used in Example 2 except that 0.59 grams of the final liquid product mixture of Example 7 containing the vanadium organo-metallic compound I dissolved therein diluted with 30 cc of benzene were used. The difference in the amount of the solution of catalyst component used in this Example versus that of the solid vanadium organophosphate catalyst component used in Example 2 was the amount necessaryto put themon an equivalent vanadium content. The yield of the vanadium coordination catalyst of this invention was 91 grams. This yield correspondsvto a productivity of about 245 grams of polymer product per .gram of the solid vanadium organometallic compound of this invention or about 21,800 grams of polymer product per gram of vanadium.

EXAMPLE 9 Use of Vanadyl Sulfate as a Catalyst Component in Preparation of EP Rubber. at 25C as a Control 0.16 grams of vanadyl sulfate slurried'with 30 cc of 40 I vacuum stripped at 10 mm Hg. and about 120 C to mineral oil were used in place of the hydrocarbon soluble vanadium organometallic compound of this invention and the procedure of Example 2 wasfollowed to yield only a trace of EP rubber product.

EXAMPLE l0 Use of the Solution of Vanadium-Organometallic Component of Example 7 in the Preparation of EPDM Rubber in a Continuous Run A feed vessel was charged with 2250 cc of n-heptane and 2.8 grams of ehtylaluminum sesquichloride. A glass-bowl reactor was flushed with ethylene and charged with 30 psi of ethylene, 750 cc of the mixture from the feed vessel and 300 cc of liquid propylene. A continuous feed stream of ENB dissolved in 30 cc of nheptane and the final liquid productmixture of Example 7 diluted with 30 cc of benzene were continuously added during the course of this continuous run in the presence of hydrogen at a pressure of about 100 psig and at a temperature of C. After a minute tinitiation period, the liquid level in the reactor 'was maintained at 1300 cc by slowly discharging the contents.

The total reaction time for the continuous run was90 minutes. The total feed added during this period and the resulting EPDM rubber properties are indicated in Table l-below:

TABLE I Total Feed Solution of vanadium catalyst component 0.52 grams Ethylaluminum sesquichloride 2.8 grams Hydrogen 4.5 liters Ethylene 99. liters Propylene 900. cc Ethylidene norbomene l8. cc n-heptane 2250. cc EPDM PRODUCT Yield 143 grams Productivity 435 grams product/gm. solid catalyst EXAMPLE 11 Preparation of Solid Vanadium Organometallic and Sulfur Dioxide To a one liter reactor equipped with a condenser, a mechanical stirrer and an adapter for gas addition were added 46.8 grams (0.4 mole) of ammonium meta vanadate (NI-I VO and 728.8 grams (4 moles) of triethyl phosphate. Sulfur dioxide was continuously purged into the reactor for a period of about 9 hours. The temperature of the reactants was held at about 48 C for'about 12 hour and then in the range of about 55 to C for about 4 hours whereupon the reaction mixture turned from a light green to yellow. The mixture was maintained in the range of to 87 C for 5 hours without visible change in the color of the reactants and the SO, purge was terminated. The reaction mixture was then held at 1 10 C for an additional 3 hour period to result in a brown mixture. The resulting product mixture was filtered to yield 50 grams of solid residue and 688.5 grams of light green filtrate. The filtrate was yield a thick syrup. 500 ml of n-heptane were-added to the thick syrup from which were recovered 26.2 grams of green solids. The solid residue was dissolved in 1 liter of benzene and the resulting solution was heated to 60 C and held at this temperature for 1 hour. The benzene was stripped to produce an additional 13.3v grams of green solids" crystals which were recrystallized in benzene. A portion of the green solids was recrystallized from n-heptane to yieldthe same blue prismatic crystals, characteristic of the vanadium organo-metallic catalyst component produced by the-procedure of Example 1.

The foregoing examples have illustrated the alternate routes to the synthesis of hydrocarbon soluble vanadium organo-metallic catalyst components and their use in active vanadium coordination polymerization catalysts. These components have been shown to be highly effective whether employed in asolution of the organophosphate or as a crystalline solid.

What is claimed is: 1. A composition of matter comprising the reaction product of:

a. a vanadium salt of inorganic acids containing sulfur and oxygen'or the double salts of vanadium sulfates with the sulfates of alkali metals or ammonia,

b. an organophosphate compound having the formui (R)|i 4. A composition of matter comprising the reaction product of:

a. a vanadium salt of inorganic acids containing sulfur and oxygen or the double salts of vanadium sulfates with the sulfates of alkali metals or ammonia,

b. an organophosphate compound having the formuwherein-R is an alkyl having one to eight carbon atoms. 

2. The composition of claim 1 wherein said vanadium salt is vanadyl sulfate.
 3. The composition of claim 1 wherein said reaction product is produced from one mole of said vanadium salt and at least two moles of said organophosphate compound.
 4. A composition of matter comprising the reaction product of: a. a vanadium salt of inorganic acids containing sulfur and oxygen or the double salts of vanadium sulfates with the sulfates of alkali metals or ammonia, b. an organophosphate compound having the formula: 